JPH06255048A - Multi-layered molded body - Google Patents

Abstract

PURPOSE:To provide a multi-layered molded body that is less susceptible to the deformation due to thermal expansion and contraction, and has excellent weatherability and durability. CONSTITUTION:The multi-layered molded body 1 comprises a layer 13 consisting of acrylic resin provided on one surface of a layer 11 consisting of polyolefine via an adhesive 12. Herein, adhesive layer forming resin is used. In which epoxy modified polypropylene is added on ethylene-methylmethacrylate (EMMA) at a rate of 100:0.4 in weight ratio.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin layer which is used outdoors such as rain gutters, window frames, corrugated boards, deck materials, and side protectors for automobiles and which has little deformation due to thermal expansion and contraction and has excellent weather resistance. The present invention relates to a multi-layer molded article that is provided with and has excellent durability.

[0002]

2. Description of the Related Art Conventionally, as a method of coating a layer made of polypropylene with a resin layer having excellent weather resistance, for example, as described in Japanese Patent Publication No. 60-42029, a polyolefin synthetic resin layer and an acrylic resin layer are multilayered. It has been proposed to use a block copolymer composed of a monovinyl-substituted aromatic compound and a conjugated diene as an intermediate layer polymer for adhering both layers during composite molding.

Further, as described in JP-B-49-35341, an ethylene-vinyl acetate copolymer / vinyl chloride copolymer (hereinafter referred to as EVA / VC graft copolymer).
A method for laminating and adhering an acrylic resin film containing a polyolefin and a polyolefin has been proposed.

[0004]

However, in the former case, the block copolymer comprising the monovinyl-substituted aromatic compound and the conjugated diene as the intermediate layer polymer is used for the polyolefin synthetic resin layer and the acrylic resin layer. Since the adhesiveness is not sufficient, there is a problem that the polyolefin synthetic resin layer and the acrylic resin layer are easily separated. In the latter case, the EVA / VC graft copolymer is inferior in heat resistance, resulting in poor thermal stability during molding, and discoloration when the obtained laminate is used outdoors for a long period of time. However, there is a problem that the physical properties tend to deteriorate.

The present invention solves the problems of the prior art,
A layer made of a polyolefin that is less deformed by thermal expansion and a layer made of an acrylic resin having improved weather resistance, which is a disadvantage of the layer made of a polyolefin, are bonded to each other via an adhesive layer having excellent adhesive strength. Thus, the object is to provide a multilayer molded body which is less likely to be thermally deformed by thermal expansion and contraction, is excellent in weather resistance, and is excellent in durability.

[0006]

The present invention is a multi-layer molded article in which a layer made of an acrylic resin is provided on a layer made of a polyolefin via an adhesive layer, wherein the adhesive layer is an ethylene-acrylic acid ester. Copolymer, unsaturated carboxylic acid modified polyolefin, epoxy modified polyolefin,
It is a multi-layer molded article composed of one or more polyolefins selected from the group consisting of silanol-modified polyolefins.

In the present invention, the polyolefin forming the layer composed of polyolefin includes homopolymers and copolymers of α-olefin, copolymers of α-olefin and diolefin, and α-olefin and unsaturated carboxylic acid. A copolymer with an ester or the like is used.

The α-olefin homopolymers and copolymers include, for example, polyethylene, polypropylene, polybutene, polyhexene, polyoctene, polydecene,
Ethylene-propylene copolymer, ethylene-butene-1
Examples thereof include copolymers and ethylene-4-methylpentene-1 copolymers.

Examples of the copolymer of α-olefin and diethylene include ethylene-butadiene copolymer and propylene-butadiene copolymer. Examples of the copolymer of α-olefin and unsaturated carboxylic acid ester include ethylene-vinyl acetate copolymer and propylene-vinyl acetate copolymer. These polyolefins may be used alone or in combination of two or more.

In the present invention, in the polyolefin,
Glass fibers and inorganic fillers can be added if necessary.

In the present invention, the acrylic resin forming the layer made of acrylic resin is a polymethylmethacrylate homopolymer, methylmethacrylate as a main component, methyl acrylate, ethyl acrylate, n-butyl methacrylate, lauryl methacrylate. Is a copolymer containing a small amount of other copolymerizable monomers such as, and belongs to the thermoplastic resin region, and preferably has an average molecular weight of 100,000-6.
One of 0,000 is used.

In the present invention, ethylene is contained in the adhesive layer.
Contains an acrylic acid ester copolymer. As the ethylene-acrylic acid ester copolymer, a copolymerized acrylic acid ester copolymer containing polymethylmethacrylate alone or methylmethacrylate as a main component and a small amount of other copolymerizable monomers such as methyl acrylate and ethyl acrylate is used. A copolymer of a polymer and an ethylene component, which is a copolymer resin of ethylene and methacrylic acid generally called EMMA and EMAA, in which a carboxyl group randomly present in a molecular chain is a molecule by a hydrogen bond. In addition to those crosslinked in the inner chain, those crosslinked with metal ions and those having a portion crosslinked with metal ions are used.

The content of acrylic acid ester in the ethylene-acrylic acid ester copolymer is preferably 5 to 50% by weight. If the content is less than 5% by weight, the adhesive force with the polar resin tends to be poor, and conversely, if it exceeds 50% by weight, it tends to be rigid and the adhesiveness tends to be poor.

In the present invention, the adhesive layer contains at least one polyolefin selected from the group consisting of unsaturated carboxylic acid modified polyolefin, epoxy modified polyolefin and silanol modified polyolefin.

The unsaturated carboxylic acid-modified polyolefin is one in which an unsaturated carboxylic acid or its derivative is added to the polyolefin. Examples of unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid (registered trademark). Examples of the unsaturated carboxylic acid derivative include acid halides such as maleenyl chloride, acid imides such as maleimide, maleic anhydride, acid anhydrides such as citraconic anhydride, monomethyl maleate, dimethyl maleate and esters such as glycidyl maleate. Is mentioned.

There are various known addition methods, for example, a method in which a radical initiator is added to a polyolefin such as maleic anhydride in the presence or absence of a catalyst, and heat treatment is carried out. , Unsaturated carboxylic acid or its derivative, peroxide (radical generator)
And a method of carrying out a kneading reaction with the above.

Examples of the epoxy-modified polyolefin include those obtained by adding diepoxy side with bisphenol A and epichlorohydrin to the polyolefin. Various well-known methods can be adopted as the adding method.

As the silanol-modified polyolefin,
Examples include those obtained by adding a reactive (polymerizable) silane such as vinylmethoxysilane or vinylethoxysilane to a polyolefin, or by copolymerizing a reactive low-molecular olefin and a reactive (polymerizable) silane. To be

The polyolefin to which these additional components are added is preferably a resin of the same type as the polyolefin forming the adherend layer (for example, polypropylene when the resin of the coating layer is polypropylene) because of its good adhesiveness, and its molecular weight ( The weight average molecular weight) is preferably about 500,000 or less because the dispersion compatibility with the ethylene-acrylic acid ester copolymer is excellent.

As the addition state of the additional component to the polyolefin, graft polymerization is preferable because addition of a small amount improves the adhesiveness, but it may be added in a block-like random form. The addition amount of the additional component to the polyolefin is preferably 0.3% by weight or more based on the polyolefin.
If the amount added falls below this range, the adhesion with the polar resin tends to be poor.

A second aspect of the present invention is a multi-layer molded article in which a layer made of an acrylic resin is provided on a layer made of a polyolefin via an adhesive layer, wherein the adhesive layer is a mixture of a styrene elastomer and a chlorinated polyolefin. It is a multi-layer molded article comprising at least one adhesive selected from the group consisting of chlorinated styrene elastomer, styrene elastomer and epoxy-modified polyolefin, and epoxy-modified styrene elastomer.

In the second aspect of the present invention, the same polyolefin as that of the present invention is used as the polyolefin forming the layer of polyolefin and the aryl resin forming the layer of acrylic resin.

In the present invention 2, included in the adhesive layer,
Examples of the styrene elastomer include and
Styrene-butadiene-styrene copolymer (SBS),
Styrene-isoprene-styrene copolymer (SIS),
Styrene obtained by hydrogenating them-ethylene /
Butadiene-styrene copolymer (SEBS), styrene-ethylene / propylene-styrene copolymer (SEP)
S) and the like.

As the styrene elastomer, those having a rubber component content of 30 to 90% by weight other than the styrene component in the copolymer are preferably used. Content of rubber component is 30
If it is less than wt%, elasticity tends to be lost. On the contrary, if it exceeds 90 wt%, the tensile strength tends to decrease, and the adhesive strength tends to decrease.

In the above, the chlorinated polyolefin mixed with the styrenic elastomer has a chlorination degree of 20.
Those of -40% are preferably used. Chlorination degree is 20%
If it is less than 40%, the adhesiveness to the layer made of an acrylic resin tends to be lowered, and conversely, if it exceeds 40%, the adhesiveness to the layer made of polyolefin tends to be lowered.

The amount of chlorinated polyolefin added is 40 to 200 with respect to 100 parts by weight of the styrene elastomer.
Weight parts are preferred. When the addition amount is less than 40 parts by weight, the adhesiveness with the layer made of an acrylic resin decreases, and conversely, when it exceeds 200 parts by weight, the adhesiveness with the layer made of a polyolefin tends to decrease. is there.

As the chlorinated styrene elastomer for forming the adhesive layer, those having a chlorination degree of 20 to 40% are preferably used. If the degree of chlorination is less than 20%, the adhesiveness with the layer made of an acrylic resin decreases, and conversely, 40%
If it exceeds%, the adhesiveness to the layer made of polyolefin tends to decrease.

The same epoxy-modified polyolefin as that used in the present invention is used as the epoxy-modified polyolefin mixed with the styrene elastomer for forming the adhesive layer. As the epoxy-modified styrene-based elastomer for forming the adhesive layer,
For example, those obtained by adding diepoxy side or the like with glycidyl (meth) acrylate to a styrene-based elastomer can be cited. Various well-known methods can be adopted as the adding method.

The composition for forming the adhesive layer includes:
These compositions may be used alone or in combination of two or more.

The present invention will be described below with reference to the drawings.
FIG. 1 is a sectional view showing an example of the multilayer molded body of the present invention. In FIG. 1, reference numeral 1 denotes a multilayer molded body, in which a layer 13 made of acrylic resin is provided on one surface of a layer 11 made of polyolefin via an adhesive layer 12 and integrally cured. Although not particularly shown, the multilayer molded body may be integrally cured by providing a layer made of an acrylic resin on both sides of a layer made of a polyolefin via adhesive layers.

[0031]

In the multilayer molded article of the present invention, since the layer made of polyolefin has a small linear expansion coefficient, it is provided with the layer made of an acrylic resin which is less deformed by thermal expansion and contraction and has excellent weather resistance. The adhesive layer is selected from the group consisting of an ethylene-acrylic acid ester copolymer, an unsaturated carboxylic acid-modified polyolefin, an epoxy-modified polyolefin and a silanol-modified polyolefin. Since it is composed of one or more kinds of polyolefins, the layer composed of the polyolefin and the layer composed of the acrylic resin having a polar group are adhered to each other by an adhesive layer having an excellent adhesive property, so that the layers are separated by thermal expansion and contraction. It is durable enough to be used outdoors for a long time.

In the multilayer molded article of the present invention 2, since the layer made of polyolefin has a small coefficient of linear expansion, the layer made of an acrylic resin excellent in weather resistance and less deformed by thermal expansion and contraction is provided. The layer consisting of is improved in weather resistance, and the adhesive layer is a mixture of a styrene elastomer and a chlorinated polyolefin, a chlorinated styrene elastomer, a styrene elastomer and an epoxy-modified polyolefin, and an epoxy-modified styrene-based adhesive. Since it comprises at least one kind of adhesive selected from the group consisting of elastomers, the layer made of polyolefin and the layer made of acrylic resin having a polar group are adhered to each other by an adhesive layer having excellent adhesiveness. It can be used outdoors for a long time without delamination due to thermal expansion and contraction. It has a durability.

[0033]

EXAMPLES The present invention will be described below with reference to examples. Example 1 As a resin for forming a layer made of polyolefin, polypropylene [trade name "EC-8" manufactured by Mitsubishi Yuka, MFR
(230 ° C.) = 1.5] was used.

As a resin for forming a layer made of an acrylic resin, polymethylmethacrylate (hereinafter abbreviated as PMMA) [Sumika Haas Co., Ltd., trade name "HFJ-10", MF
R (230 ° C.) = 4] was used. As a composition for forming an adhesive layer, an ethylene-methyl methacrylate copolymer (hereinafter abbreviated as EMMA) (Sumitomo Chemical Co., Ltd., trade name "Acryft", acrylic content 15%), epoxy-modified polypropylene (Nippon Yushi Co., Ltd.) , Trade name "Blenmer", polypropylene weight average molecular weight 9000, epoxy equivalent 5
29) was added at a weight ratio of 100: 0.4.

Using three twin-screw extruders in the same direction, the layer forming resin made of polyolefin, the adhesive layer forming composition, and the layer forming resin made of acrylic resin were kneaded and melted in the extruder and extruded, In a multi-layer mold, a layer made of acrylic resin is laminated on a layer made of polyolefin via an adhesive layer, and the thickness of the layer made of polyolefin / the adhesive layer / the layer made of the acrylic resin is 100 μm / 50.
A multilayer molded body having a thickness of μm / 1.3 mm was obtained. The thermal stability of the resin during formation was evaluated.

A test piece was cut out from the obtained multilayer molded article, and the adhesive strength was evaluated by a 180 ° peel test.
The thermal stability and adhesive strength are shown in Table 1. Regarding the thermal stability, the one in which the resin does not decompose during molding is indicated by ◯, and the one by which the resin decomposed is indicated by ×. Regarding the adhesive strength, a test piece as shown in FIG. 2 was prepared, and the test was performed in accordance with JIS K 6854 under the conditions of a tensile speed of 5 mm / min and a test temperature of 23 ° C.

Example 2 As a resin for forming a layer composed of polyolefin, polypropylene [made by Mitsubishi Yuka, trade name "XIA", MFR (2
30 ° C.) = 1.0], and as a composition for forming an adhesive layer, EMMA (manufactured by Sumitomo Chemical Co., Ltd., trade name “Acryft”, acrylic content 15%) and maleic acid-modified polypropylene in a weight ratio. Example 1 was repeated in the same manner as in Example 1 except that the mixture added at a ratio of 90:10 was used.
A multilayer molded body having the same size as was obtained. As in Example 1, the results of evaluating thermal stability and tensile strength are shown in Table 1.

As the maleic acid-modified polypropylene, polypropylene [trade name "BC3 manufactured by Mitsubishi Yuka Co., Ltd.
B ”, MFR (230 ° C.) = 9.0] to which maleic anhydride was added at a weight ratio of 99: 1, a radical initiator (manufactured by NOF Corporation, trade name“ Park Mill H ”) was added. What was added 0.4 parts by weight to 100 parts by weight of polypropylene was put into a hopper, kneaded and melted in an extruder, extruded, cooled, and then pelletized.

Example 3 As a composition for forming an adhesive layer, an ethylene-methyl acrylate copolymer (hereinafter abbreviated as EMAA) (manufactured by Mitsui DuPont Chemical Co., trade name "Nucrel", methyl acrylate content 12% by weight) ) Was used in the same manner as in Example 1 except that a silanol-modified polypropylene was added at a weight ratio of 80:20 to obtain a multilayer molded article having the same dimensions as in Example 1. As in Example 1, the results of evaluating thermal stability and tensile strength are shown in Table 1.

As the silanol-modified polypropylene, polypropylene [trade name "BC3 manufactured by Mitsubishi Yuka Co., Ltd.
B ”, MFR (230 ° C.) = 9.0] to which reactive (polymerizable) silane (Shin-Etsu Silicone Co., vinyl methoxysilane) was added at a weight ratio of 95: 5 to a radical initiator. (Nippon Yushi Co., Ltd., trade name "Park Mill H",
Hydroperoxide) was added in an amount of 0.04 parts by weight to 100 parts by weight of polypropylene, which was put into a hopper, kneaded and melted in an extruder, extruded, cooled, and then pelletized.

Comparative Example 1 As a composition for forming an adhesive layer, a styrene-ethylene / butadiene-styrene block copolymer (hereinafter abbreviated as SEBS) (manufactured by Asahi Kasei Corporation, trade name "H1041", styrene / ethylene butadiene = 30) A multilayer molded body was obtained in the same manner as in Example 1 except that the ratio of / 70) was used. Implementation 1
Table 1 shows the results of evaluation of thermal stability and tensile strength in the same manner as in.

Comparative Example 2 As a composition for forming an adhesive layer, a styrene-ethylene / propylene-styrene block copolymer (hereinafter abbreviated as SEPS) (Asahi Kasei Co., Ltd., trade name "H1041", styrene / ethylene butadiene = 30) / 70) was used in the same manner as in Example 1 to obtain a multilayer molded article having the same dimensions as in Example 1. As in Example 1, the results of evaluating thermal stability and tensile strength are shown in Table 1.

Comparative Example 3 The procedure of Example 1 was repeated except that the epoxy-modified polypropylene was not added to the adhesive layer-forming composition.
A multilayer molded body having the same size as in Example 1 was obtained. As in Example 1, the results of evaluating thermal stability and tensile strength are shown in Table 1.

Comparative Example 4 As a composition for forming an adhesive layer, an ethylene-vinyl acetate copolymer / vinyl chloride graft copolymer (hereinafter referred to as EVA / V
A multilayer molded article was obtained in the same manner as in Example 1 except that C graft copolymer was used). As in Example 1, the results of evaluating thermal stability and tensile strength are shown in Table 1.

[0045]

[Table 1]

Examples 4 to 6 As a composition for forming an adhesive layer, a predetermined amount of chlorinated polyethylene shown in Table 2 of SEBS (manufactured by Asahi Kasei Co., Ltd., trade name "H1041", styrene / ethylene butadiene = 30/70). (Made by Tokuyama Sekisuisha, product name "Esmic CE535
A ", chlorination degree 35%) was used in the same manner as in Example 1 except that the predetermined amount shown in Table 2 was added to obtain a multilayer molded article. The results of evaluating the tensile strength are shown in Table 2 as in Example 1.

Example 7 As a composition for forming an adhesive layer, 100 parts by weight of SEPS (manufactured by Asahi Kasei Co., Ltd., trade name "H1041", styrene / ethylene butadiene = 30/70) was added to chlorinated polyethylene (manufactured by Tokuyama Sekisui Co., Ltd., A multilayer molded product was obtained in the same manner as in Example 1 except that 100 parts by weight of the product name Esmic CE535A, chlorination degree 35%) was added. Implementation 1
Table 2 shows the results of evaluation of tensile strength in the same manner as in.

Example 8 A multilayer molded article was obtained in the same manner as in Example 1 except that chlorinated SEBS (chlorination degree: 35%) was used as the composition for forming an adhesive layer. The results of evaluating the tensile strength are shown in Table 2 as in Example 1.

As the chlorinated SEBS, SEBS
(Asahi Kasei Co., Ltd., trade name “H1041”, styrene / ethylene butadiene = 30/70) 2000 g and carbon tetrachloride 3.21 g of a uniform solution, under a nitrogen atmosphere in a reaction kettle at a temperature of 50 ° C. and ultraviolet rays. 1.55g of chlorine gas while irradiating (UV fluorescent lamp wavelength 340-700nm)
After the introduction at a rate of / min, carbon tetrachloride was replaced with ethyl acetate to obtain the product.

Example 9 A multilayer molded article was obtained in the same manner as in Example 1 except that chlorinated SEPS (chlorination degree: 35%) was used as the composition for forming an adhesive layer. The results of evaluating the tensile strength are shown in Table 2 as in Example 1.

As chlorinated SEPS, SEPS
(Asahi Kasei Co., Ltd., trade name “H1041”, styrene / ethylene butadiene = 30/70) 2000 g and carbon tetrachloride 3.21 g of a uniform solution, under a nitrogen atmosphere in a reaction kettle at a temperature of 50 ° C. and ultraviolet rays. 1.55g of chlorine gas while irradiating (UV fluorescent lamp wavelength 340-700nm)
After the introduction at a rate of / min, carbon tetrachloride was replaced with ethyl acetate to obtain the product.

Example 10 As a composition for forming an adhesive layer, 100 parts by weight of SEBS (manufactured by Asahi Kasei Co., Ltd., trade name "H1041", styrene / ethylene butadiene = 30/70) was added with epoxy-modified polypropylene (manufactured by NOF CORPORATION, Product name "Blenmer", polypropylene weight average molecular weight 9000, epoxy equivalent 52
9) A multilayer molded product was obtained in the same manner as in Example 1 except that 0.4 part by weight was added. The results of evaluating the tensile strength are shown in Table 2 as in Example 1.

Example 11 A multilayer molded article was obtained in the same manner as in Example 1 except that epoxy modified SEBS was used as the adhesive forming composition. The results of evaluating the tensile strength are shown in Table 2 as in Example 1.

As the epoxy-modified SEBS, SE
BS (Asahi Kasei Corp., trade name "H1041", styrene /
To 100 parts by weight of ethylene / butadiene = 30/70), 0.1 parts by weight of glycidyl acrylate was added, respectively, and a radical initiator (trade name “Park Mill H” manufactured by NOF CORPORATION, hydroperoxide) was added. 3 parts by weight of bisphenol A (97 parts by weight) was added to a hopper, kneaded and melted in an extruder, extruded, cooled, and then pelletized.

[0055]

[Table 2]

[0056]

EFFECTS OF THE INVENTION Since the multi-layer molded article of the present invention and the present invention 2 are constructed as described above, they are less deformed by thermal expansion and contraction, have improved weather resistance, and a layer made of polyolefin, The layers made of acrylic resin with polar groups are adhered to both layers by an adhesive layer with excellent adhesiveness, and the layers do not peel off due to thermal expansion and contraction, and are durable enough to be used outdoors for a long time Is equipped with.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a multilayer molded body of the present invention.

FIG. 2 is a front view showing a test piece for a 180 ° peel test.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Multilayer molded body 11 Layer made of polyolefin 12 Adhesive layer 13 Layer made of acrylic resin

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08J 5/12 CEY 9267-4F

Claims (2)

[Claims] 1. A multi-layered molded product comprising a layer of polyolefin and a layer of acrylic resin provided via an adhesive layer, wherein the adhesive layer comprises an ethylene-acrylic acid ester copolymer and an unsaturated carboxylic acid. A multilayer molded article comprising one or more polyolefins selected from the group consisting of acid-modified polyolefins, epoxy-modified polyolefins, and silanol-modified polyolefins. 2. A multilayer molded article comprising a layer made of polyolefin and a layer made of an acrylic resin provided via an adhesive layer, wherein the adhesive layer is a mixture of a styrene elastomer and a chlorinated polyolefin, and is chlorinated. A multilayer molded article comprising a styrene-based elastomer, a mixture of a styrene-based elastomer and an epoxy-modified polyolefin, and at least one adhesive selected from the group consisting of epoxy-modified styrene-based elastomers.